Doubled reactive dyes

ABSTRACT

Reactive dyes of the formula ##STR1## where R 1  is hydrogen, methyl or ethyl, 
     X is hydrogen or hydroxysulfonyl, 
     Hal is fluorine or chlorine, 
     D is phenylene, carboxyl- or hydroxysulfonyl-monosubstituted or -disubstituted phenylene or hydroxysulfonyl-monosubstituted or -disubstituted naphthylene, 
     A is a fiber-reactive radical, or A--D combined is a benzo-fused fiber-reactive radical, and 
     Z is a bridge member, are useful for dyeing or printing hydroxyl- or nitrogen-containing substrates.

This application is a continuation of application Ser. No. 07/489,982, filed Feb. 20, 1990, now abandoned.

The present invention relates to novel reactive dyes of the formula I ##STR2## where R¹ is hydrogen, methyl or ethyl,

X is hydrogen or hydroxysulfonyl,

Hal is fluorine or chlorine,

D is phenylene, carboxyl- or hydroxysulfonyl-monosubstituted or -disubstituted phenylene or hydroxysulfonyl-monosubstituted or -disubstituted naphthylene,

A is a fiber-reactive radical, or A--D combined is a benzo-fused fiber-reactive radical, and

Z is a bridge member of the formula ##STR3## where R² is C₁ -C₄ -alkyl.

JP-A-27 628/1978 and DE-A-3 135 432 disclose reactive dyes which are similar to those of the formula I. However, they differ in the bridge member Z which joins the two chromophore radicals together

It has been found that the prior art dyes still have application defects.

It is an object of the present invention to provide new reactive dyes having advantageous properties, in particular a high fixation efficiency.

We have found that this object is achieved by the reactive dyes of the formula I defined in more detail at the beginning.

R² in the formula I is for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.

D is for example ##STR4##

Fiber-reactive radicals A are those which react substitutively or additively with the hydroxyl- or nitrogen-containing groups of the substrates to be treated. The fact that the reactive radical A reacts substitutively with the relevant groups in the substrates, for example with the hydroxyl groups of cellulose, means that the leaving groups or atoms (for example fluorine or chlorine) are replaced in the fiber-reactive radical A by the hydroxyl groups of the cellulose in accordance with the following scheme: ##STR5##

The fact that the fiber-reactive radical A reacts additively with the relevant groups in the substrates, for example with the hydroxyl groups of cellulose, means that the hydroxyl groups of the cellulose are added to the fiber-reactive radical in accordance with the following scheme: ##STR6##

Fiber-reactive radicals A are for example vinylsulfonyl, 2-hydroxyethylsulfonyl radicals which are esterified with polybasic inorganic acids and form vinylsulfonyl under dyeing conditions, halogen-substituted radicals of 1,3,5-triazine, quinoxaline, phthalazine, pyrimidine or pyridazone, and the 2-alkylsulfonylbenzothiazole radical.

Examples are the following radicals: --SO₂ --C₂ H₄ OSO₃ H, --SO₂ --C₂ H₄ OPO₃ H₂, ##STR7## where Hal is fluorine or chlorine and R³ is hydrogen or nitro and the rings B and C may each be substituted by hydroxysulfonyl and the ring C independently thereof by chlorine, nitro, by up to two methoxy groups or by up to three C₁ -C₄ -alkyl groups.

If the radical A--D is a benzo-fused reactive radical, a possibility is for example the 2-alkylsulfonylbenzothiazole radical. Examples are the radicals ##STR8##

Radicals of the coupling components of the formula ##STR9## are for example ##STR10## where R¹ is hydrogen, methyl or ethyl.

Preference is given to reactive dyes of the formula I where A is a radical of the formula ##STR11## where Hal is as defined above, R⁴ is hydrogen or C₁ -C₄ -alkyl,

R⁵ is hydrogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy and

R⁶ is hydrogen, C₁ -C₄ -alkyl or hydroxysulfonyl.

Preference is further given to reactive dyes of the formula I where D is the radical ##STR12##

Preference is further given to reactive dyes of the formula I where the radical ##STR13##

Preference is further given to reactive dyes of the formula I where the bridge member Z conforms to the formula Z¹ and is the radical ##STR14## where R² is in each case as defined above.

Particular preference is given to reactive dyes of the formula Ia ##STR15## where X is hydrogen or hydroxysulfonyl and Z¹ is as defined above.

Particular preference is further given to reactive dyes of the formula Ib ##STR16## where Hal is fluorine or chlorine,

R⁴ is hydrogen or C₁ -C₄ -alkyl,

R⁵ is hydrogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy,

R⁶ is hydrogen, C₁ -C₄ -alkyl or hydroxysulfonyl,

X is hydrogen or hydroxysulfonyl, and

Z¹ is as defined above.

Particular preference is further given to reactive dyes which conform to the formula Ic ##STR17## where Z¹ is as defined above.

Particular preference is further given to reactive dyes which conform to the formula Id ##STR18## where Hal is fluorine or chlorine,

R⁴ is hydrogen or C₁ -C₄ -alkyl,

R⁵ is hydrogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy,

R⁶ is hydrogen, C₁ -C₄ -alkyl or hydroxysulfonyl, and

Z¹ is as defined above.

Of particular note are reactive dyes of the formula Ib where R⁴ and R⁵ are each hydrogen and R⁶ is hydroxysulfonyl or where R⁴ is hydrogen, R⁵ is o,o'-C₁ -C₂ -alkyl and R⁶ is methyl or hydrogen.

The novel reactive dyes of the formula I are prepared in a conventional manner.

For example,

a) an amine of the formula II

    A--D--NH.sub.2                                             (II)

where A and D are each as defined above, can be diazotized and coupled with a coupling component of the formula III ##STR19## where R¹, X, Z and Hal are each as defined above.

A further method comprises for example diazotizing

b) an amine of the formula II and coupling it with a coupling component of the formula IV ##STR20## where R¹, X and Hal are each as defined above, and reacting the product with a compound of the formula V

    ZH.sub.2                                                   (V)

where Z is as defined above.

A further method comprises for example diazotizing

c) an amine of the formula VI ##STR21## where Hal and D are each as defined above, coupling it with a coupling component III and optionally reacting the product with an aniline derivative of the formula VII ##STR22## where R⁴ and the ring C are each as defined above.

The novel reactive dyes of the formula I are advantageously suitable for dyeing or printing hydroxyl- or nitrogen-containing organic substrates. Such substrates are for example leather and fiber material which predominantly contain natural or synthetic polyamides or natural or regenerated cellulose The novel dyes are preferably used for dyeing and printing textile material based on cotton. Used in this way, they are notable for high fixation efficiencies.

The following Examples will further illustrate the invention:

EXAMPLE 1

a) An ice-cold suspension of 2-methylamino-5-aminobenzenesulfonic acid was prepared by acidifying a solution of 63 g of the sodium salt in 1000 ml of ice-water (down to pH 2), and 111 g of cyanuric chloride were added. 77 g of sodium bicarbonate were sprinkled in to adjust the pH to 5, and the suspension was subsequently stirred at 0°-5° C. for 3 hours until acylation of the amino groups was complete. The suspension of the bisacyl compound was then admixed with a solution of 191 g of 1-aminonaphth-8-ol-3,6-disulfonic acid in 400 ml of water and 35 ml of 50% strength by weight sodium hydroxide solution, brought to pH 5 and stirred at 40° C. for three hours. A small amount of suspended solids was then filtered off and the product of the formula ##STR23## was precipitated with 600 g of sodium chloride. The precipitate was filtered off with suction, washed with 15% strength by weight sodium chloride solution and used in the form of a moist presscake for processing into the dyes described hereinafter. The crude yield was 91% of theory as tetrasodium salt.

b) 14.1 g (0.05 mol) of 4-(2-sulfatoethylsulfonyl)aniline were dissolved with 10 ml of saturated sodium acetate solution in 150 ml of water at room temperature and cooled by stirring with 75 g of ice in an icebath. 15 ml of 3.33N aqueous sodium nitrite solution and 15 ml of 30% strength by weight hydrochloric acid were then simultaneously added dropwise, and the suspension was subsequently stirred at 0°-5° C. for about an hour. After excess nitrous acid had been destroyed with sulfamic acid, the suspension was admixed with a solution of 0.024 mol of the coupling component of a) in 200 ml of water. The coupling was carried out by the dropwise addition of 15 ml of saturated sodium acetate solution (down to pH 2) and two hours' stirring with warming to room temperature. The resulting dye of the formula ##STR24## was precipitated with 150 g of potassium chloride, filtered off with suction, washed with acetone and dried at room temperature under reduced pressure

Applied to cotton from an alkaline bath, it produces bluish red dyeings over a wide temperature range, starting from room temperature, with very high dyeing efficiency.

EXAMPLE 2

a) A solution of 0.38 mol of 1-aminonaphth-8-ol-3,6-disulfonic acid in 250 ml of water and 21 ml of 50% strength by weight sodium hydroxide solution was added to a thoroughly stirred suspension of 73.8 g (0.4 mol) of cyanuric chloride in 450 ml of ice-water and 5 ml of 30% strength by weight hydrochloric acid, and the mixture was subsequently stirred at 5°-8° C. for 2.5 hours until acylation of the aminonaphthalene was complete. This solution was then admixed with a solution of 34 g (0.18 mol) of 3,5-diaminobenzene-1-sulfonic acid in 200 ml of water and 10 ml of 50% strength by weight sodium hydroxide solution and adjusted to pH 5 with 20% strength by weight ice-cold sodium hydroxide solution. After stirring overnight at pH 5 and room temperature, the resulting product of the formula ##STR25## was filtered off with suction as the sodium salt, washed with 5% strength by weight sodium chloride solution and used in the coupling reactions described hereinafter. The yield of crude product was 93% of theory.

b) 20.3 g (0.05 mol) of 2-(N-methyl-N-phenylamino)-4-chloro-6-(3'-amino-4'-hydroxysulfonylphenylamino)-s-triazine were dissolved with sodium bicarbonate in 250 ml of water (to pH 7) and admixed with 15 ml of 3.33 N aqueous sodium nitrite solution. The diazotization was carried out by slowly pouring this solution into 100 g of ice and 15 ml of 30% strength by weight hydrochloric acid. After stirring in the cold for one hour, excess nitrous acid was destroyed with sulfamic acid, and the jelly-like yellowish solution was added to a suspension of 0.024 mol of the binary coupling component a) in 250 ml of water, 100 g of ice and 15 g of sodium bicarbonate. The resulting dye of the formula ##STR26## was precipitated from the solution with 100 g of sodium chloride, filtered off with suction, washed with 2.5% strength by weight sodium chloride solution and then with acetone and dried at room temperature under reduced pressure. Applied to cotton from an alkaline bath by the exhaust method at 80° C. it produces bluish red shades with a very high fixation efficiency.

The dyes listed in Table 1 below are obtained in a similar manner and likewise produce bluish to yellowish red shades with a very high dyeing efficiency.

                                      TABLE 1                                      __________________________________________________________________________      ##STR27##                                                                     Example                                             Hue on                     No.  A                     R    3-/4-SO.sub.3 H                                                                      Z             cotton                     __________________________________________________________________________      3   5-SO.sub.2C.sub.2 H.sub.4OSO.sub.3 H                                                                 H    3                                                                                     ##STR28##    red                         4   4-SOC.sub.2 H.sub.4OSO.sub.3 H                                                                       H    3                                                                                     ##STR29##    bluish red                  5                                                                                   ##STR30##            2-SO.sub.3 H                                                                        3                                                                                     ##STR31##    bluish red                  6                                                                                   ##STR32##            SO.sub.3 H                                                                          3                                                                                     ##STR33##    red                         7   4-SO.sub.2C.sub.2 H.sub.4OSO.sub.3 H                                                                 H    3                                                                                     ##STR34##    red                         8   5-SO.sub.2 C.sub.2 H.sub.4OSO.sub.3 H                                                                H    3                                                                                     ##STR35##    red                         9                                                                                   ##STR36##            2-SO.sub.3 H                                                                        3                                                                                     ##STR37##    bluish red                 10                                                                                   ##STR38##            2-SO.sub.3 H                                                                        3                                                                                     ##STR39##    red                        11                                                                                   ##STR40##            2-SO.sub.3 H                                                                        3                                                                                     ##STR41##    red                        12                                                                                   ##STR42##            2-SO.sub.3 H                                                                        3                                                                                     ##STR43##    bluish red                 13                                                                                   ##STR44##            2-SO.sub.3 H                                                                        3                                                                                     ##STR45##    bluish red                 14                                                                                   ##STR46##            2-SO.sub.3 H                                                                        3                                                                                     ##STR47##    red                        15                                                                                   ##STR48##            2-SO.sub.3 H                                                                        3                                                                                     ##STR49##    red                        16                                                                                   ##STR50##            2-SO.sub.3 H                                                                        3                                                                                     ##STR51##    bluish red                 17                                                                                   ##STR52##            2-SO.sub.3 H                                                                        3                                                                                     ##STR53##    bluish red                 18                                                                                   ##STR54##            2-SO.sub.3 H                                                                        3                                                                                     ##STR55##    red                        19                                                                                   ##STR56##            2-SO.sub.3 H                                                                        3                                                                                     ##STR57##    red                        20                                                                                   ##STR58##            2-SO.sub.3 H                                                                        3                                                                                     ##STR59##    bluish red                 21                                                                                   ##STR60##            2-SO.sub.3 H                                                                        3                                                                                     ##STR61##    red                        22                                                                                   ##STR62##            2-SO.sub.3 H                                                                        3                                                                                     ##STR63##    red                        23                                                                                   ##STR64##            2-SO.sub.3 H                                                                        3                                                                                     ##STR65##    red                        24                                                                                   ##STR66##            2-SO.sub.3 H                                                                        3                                                                                     ##STR67##    bluish red                 25                                                                                   ##STR68##            2-SO.sub.3 H                                                                        3                                                                                     ##STR69##    bluish red                 26                                                                                   ##STR70##            2-SO.sub.3 H                                                                        3                                                                                     ##STR71##    bluish red                 27                                                                                   ##STR72##            2-SO.sub.3 H                                                                        3                                                                                     ##STR73##    bluish red                 28                                                                                   ##STR74##            2-SO.sub.3 H                                                                        3                                                                                     ##STR75##    bluish red                 29                                                                                   ##STR76##            2-SO.sub.3 H                                                                        3                                                                                     ##STR77##    red                        30                                                                                   ##STR78##            2-SO.sub.3 H                                                                        3                                                                                     ##STR79##    red                        31                                                                                   ##STR80##            2-SO.sub.3 H                                                                        3                                                                                     ##STR81##    red                        32                                                                                   ##STR82##            2-SO.sub.3 H                                                                        3                                                                                     ##STR83##    red                        33                                                                                   ##STR84##            2-SO.sub.3 H                                                                        3                                                                                     ##STR85##    red                        34                                                                                   ##STR86##            2-SO.sub.3 H                                                                        3                                                                                     ##STR87##    red                        35                                                                                   ##STR88##            2-SO.sub.3 H                                                                        3                                                                                     ##STR89##    bluish red                 36                                                                                   ##STR90##            2-SO.sub.3 H                                                                        3                                                                                     ##STR91##    bluish red                 37                                                                                   ##STR92##            2-SO.sub.3 H                                                                        3                                                                                     ##STR93##    red                        38                                                                                   ##STR94##            2-SO.sub.3 H                                                                        3                                                                                     ##STR95##    red                        39                                                                                   ##STR96##            2-SO.sub.3 H                                                                        3                                                                                     ##STR97##    bluish red                 40                                                                                   ##STR98##            2-SO.sub.3 H                                                                        3                                                                                     ##STR99##    bluish red                 41                                                                                   ##STR100##           2-SO.sub.3 H                                                                        3                                                                                     ##STR101##   bluish red                 42                                                                                   ##STR102##           2-SO.sub.3 H                                                                        3                                                                                     ##STR103##   red                        43                                                                                   ##STR104##           2-SO.sub.3 H                                                                        3                                                                                     ##STR105##   red                        44                                                                                   ##STR106##           2-SO.sub.3 H                                                                        3                                                                                     ##STR107##   red                        45                                                                                   ##STR108##           2-SO.sub.3 H                                                                        3                                                                                     ##STR109##   red                        46                                                                                   ##STR110##           2-SO.sub.3 H                                                                        3                                                                                     ##STR111##   bluish red                 47                                                                                   ##STR112##           3-SO.sub.3 H                                                                        3                                                                                     ##STR113##   bluish red                 48                                                                                   ##STR114##           2-SO.sub.3 H                                                                        3                                                                                     ##STR115##   bluish red                 49                                                                                   ##STR116##           2-SO.sub.3 H                                                                        3                                                                                     ##STR117##   bluish red                 50                                                                                   ##STR118##           2-SO.sub.3 H                                                                        3                                                                                     ##STR119##   bluish red                 51                                                                                   ##STR120##           2-SO.sub.3 H                                                                        3     NHC.sub.3 H.sub.6NCH.sub.3                                                                   red                        52                                                                                   ##STR121##           H    3                                                                                     ##STR122##   violet                     __________________________________________________________________________

EXAMPLE 53

a) 21.9 g (0.14 mol) of 1-amino-3-methylaminobenzene-4-sulfonic acid (in betaine form) were dissolved with 36 ml of 10% strength by weight sodium hydroxide solution in 100 ml of water at pH 7. This solution was added to a suspension of 51.7 g of cyanuric chloride in 250 ml of ice-water and 1 ml of 30% strength by weight hydrochloric acid, and the pH was adjusted to 5 with 30 g of sodium bicarbonate. After three hours, stirring at 0°-5° C. and pH 5, a sample was no longer couplable, and the diacylaminobenzenesulfonic acid was present in solution as the sodium salt. This solution was then admixed with a solution of 0.28 mol of 1-aminonaphth-8-ol-4,6-disulfonic acid in 200 ml of water and 17 ml of 50% strength by weight sodium hydroxide solution and adjusted to pH 4 with 16 g of sodium bicarbonate with warming to room temperature. After stirring under these conditions for 4 hours, the double condensation had ended. The reaction product was precipitated at pH 1 with 400 g of potassium chloride, filtered off with suction and washed acid-free with 27% strength by weight potassium chloride solution

b) The method of Example lb was repeated to couple 4-(2-sulfatoethylsulfonyl)aniline with the coupling component of Example 53a. The result was the dye of the formula ##STR123## which dyes cotton from an alkaline bath in yellowish red shades with a high dyeing efficiency.

Similar characteristics are shown by the dyes of the formula ##STR124## which are listed in Table 2 below and which are obtained as described in Examples 1, 2 and 53.

                                      TABLE 2                                      __________________________________________________________________________     Example                                                                        No.     A                     R    3-/4-SO.sub.3 H                                                                      Z             Hue on                  __________________________________________________________________________                                                            cotton                  54   5- SO.sub.2 C.sub.2 H.sub.4OSO.sub.3 H                                                                  H    4                                                                                     ##STR125##   yellowish red           55   4- SO.sub.2 C.sub.2 H.sub.4OSO.sub.3 H                                                                  H    4                                                                                     ##STR126##   yellowish red           56   5- SO.sub.2 C.sub.2 H.sub.4OSO.sub.3 H                                                                  H    4                                                                                     ##STR127##   yellowish red           57   4- SO.sub.2 C.sub.2 H.sub.4OSO.sub.3 H                                                                  H    4                                                                                     ##STR128##   yellowish red           58   5-                                                                                 ##STR129##           2-SO.sub.3 H                                                                        4                                                                                     ##STR130##   yellowish red           59   5-                                                                                 ##STR131##           2-SO.sub.3 H                                                                        4                                                                                     ##STR132##   yellowish red           60   4-                                                                                 ##STR133##           2-SO.sub.3 H                                                                        4                                                                                     ##STR134##   yellowish red           61   5-                                                                                 ##STR135##           2-SO.sub.3 H                                                                        4                                                                                     ##STR136##   yellowish red           62   5-                                                                                 ##STR137##           2-SO.sub.3 H                                                                        4                                                                                     ##STR138##   yellowish red           63   5-                                                                                 ##STR139##           2-SO.sub.3 H                                                                        4                                                                                     ##STR140##   yellowish red           64   5-                                                                                 ##STR141##           2-SO.sub.3 H                                                                        4                                                                                     ##STR142##   yellowish red           65   5-                                                                                 ##STR143##           2-SO.sub.3 H                                                                        4                                                                                     ##STR144##   yellowish               __________________________________________________________________________                                                            red                

EXAMPLE 66

23.9 g of the sodium salt of 2-amino-5-hydroxynaphthalene-7-sulfonic acid were dissolved in 200 ml of water. This solution was added to a suspension of 18.4 g of cyanuric chloride in 150 ml of ice-water, and the mixture was adjusted to pH 3 with sodium bicarbonate. After stirring at 0°-5° C. for one hour, the mixture was filtered, and the filtrate was mixed with 10.1 g of the sodium salt of 1-methylamino-3-aminobenzene-6-sulfonic acid, dissolved in 100 ml of water. Sodium bicarbonate was then added to adjust the pH to 6, and the mixture was stirred at 45°-50° C. for 2 hours until the reaction had ended.

Coupling with 0.1 mol of a diazonium compound obtained as described in Example 1b gave the dye of the formula ##STR145## which applied to cotton from an alkaline bath at about 20°-80° C. produces orange shades with a high fixation efficiencies.

The methods of Examples 1, 2, 53 and 66 were also used to obtain the dyes of the formula ##STR146## listed in Table 3 which are likewise notable for high fixation efficiencies.

                                      TABLE 3                                      __________________________________________________________________________     Example                                                                        No.    A                     R    Z             Hue on cotton                  __________________________________________________________________________     67   5-                                                                               SO.sub.2C.sub.2 H.sub.4OSO.sub.3 H                                                                   H                                                                                    ##STR147##   orange                         68   4-                                                                               SO.sub.2C.sub.2 H.sub.4OSO.sub.3 H                                                                   H                                                                                    ##STR148##   orange                         69   5-                                                                               SO.sub.2C.sub.2 H.sub.4OSO.sub.3 H                                                                   H                                                                                    ##STR149##   orange                         70   5-                                                                                ##STR150##           2-SO.sub.3 H                                                                         ##STR151##   orange                         71   5-                                                                                ##STR152##           2-SO.sub.3 H                                                                         ##STR153##   orange                         72   5-                                                                                ##STR154##           2-SO.sub.3 H                                                                         ##STR155##   orange                         73   5-                                                                                ##STR156##           2-SO.sub.3 H                                                                         ##STR157##   orange                         __________________________________________________________________________ 

We claim:
 1. A reactive dye of the formula I ##STR158## wherein R¹ is hydrogen, methyl or ethyl,X is hydrogen or hydroxysulfonyl, Hal is fluorine or chlorine, A--D is a benzo-fused fiber-reactive group selected from the group consisting of ##STR159## Z is a bridge member of the formula ##STR160## where R² is C₁ -C₄ -alkyl.
 2. A reactive dye of the formula I ##STR161##wherein said reactive dye has (a) formula Ia ##STR162## wherein X is hydrogen or hydroxysulfonyl, (b) formula Ib ##STR163## wherein Hal is chlorine; R⁴ is hydrogen or C₁ -C₄ -alkyl; R⁵ is hydrogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; R⁶ is hydrogen, C₁ -C₄ -alkyl or hydroxysulfonyl; and X is hydrogen or hydroxysulfonyl; (c) formula Ic or ##STR164## (d) formula Id ##STR165## wherein Hal is chlorine; R⁴ is hydrogen or C₁ -C₄ -alkyl; R⁵ is hydrogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; and R⁶ is hydrogen, C₁ -C₄ -alkyl or hydroxysulfonyl; and Z is the group ##STR166## wherein R² is C₁ -C₄ -alkyl.
 3. A reactive dye as claimed in claim 1, having Formula Ia ##STR167## wherein X is hydrogen or hydroxysulfonyl.
 4. A reactive dye as claimed in claim 1, having Formula Ib ##STR168## wherein Hal is chlorine; R⁴ is hydrogen or C₁ -C₄ -alkyl; R⁵ is hydrogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; R⁶ is hydrogen, C₁ -C₄ -alkyl or hydroxysulfonyl, and X is hydrogen or hydroxysulfonyl.
 5. A reactive dye as claimed in claim 1, having Formula Ic ##STR169##
 6. A reactive dye as claimed in claim 1, having Formula Id ##STR170## wherein Hal is chlorine; R⁴ is hydrogen or C₁ -C₄ -alkyl; R⁵ is hydrogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; and R⁶ is hydrogen, C₁ -C₄ -alkyl or hydroxysulfonyl. 